Wrinkle coating from nonconjugated oils



Nov. 27, 1945. E. L. LUACES 2,389,795

WRINKLE COATING FROM NONCONJUGATED OILS Original Filed Jan 23, 1942RESERVOIR STEAM TRA INVENTOR ENmQuE L. LuA'cEs' ATTORNEY Patented Nov.27, 1945 UNITED STATES PATENT OFFICE WRINKLE COATING FROM NONCONJU-GAIED Enrique L. Luaces, Dayton, Ohio, assignor to New Wrinkle, Inc.,Wilmington, Del., a corporation I of Delaware OILS Original applicationJanuary 23, 1942, Serial No. 427,962. Divided and this applicationSeptem- .ber 19, 1942, Serial No. 459,033.

1 Claim. (01. 26022) able in large quantities from domestic sourcesandboth of which are obtained from comparatively inaccessible localitiesand are subjected to marked fluctuations in price and quality.

Both of these oils are characterized by the fact that they possess intheir structure polyconjugated double bonds. It is generally assumedthat these conjugated double bonds are responsible for the extremedrying capacity of these oils. Oiticica oil also includes in itsstructure a keto group, and it is believed that this accounts forcertain of the differences which characterize the behavior of oiticicaoil as compared with tung oil.

Tung oil and oiticica oil may be and are frequently used in theirnatural state in the production of wrinkle coating compositions;however, it is advantageous to subject them to pretreatment, as byblowing or kettling, for the purpose of either enhancing the wrinklingtenden'cy of the oil or for the purpose of reducing the cooking time andthereby increasing the output of the varnish kettles.

The nature of the pretreatment to which these oils are subjected willdepend not only on the purpose for which the oil is to be used, but alsoon the specific oil to be treated. For example, blowing will markedlyenhance the wrinkling tendency of tung oil; but, in certain instances,it would prove detrimental if applied to oiticica oil. On the otherhand, the wrinkling tendency of oiticica oil would be substantiallydestroyed it it were to be treated at temperatures such as generallyutilized in the treatment of tung oil. This is brought out in copendingapplication Serial No. 425,543, filed January 3, 1942, by W. A. Waldie.

Because of the unfavorable price and quality fluctuations of tung andoiticica oils, coupled with their limited supply and relativeinaccessibility of the crop, efforts have been made to de velopsatisfactory substitutes or replacements utilizing oils, the quality andprice of which are less subjected to fluctuations and which may beobtained plentifully from domestic sources.

For example, as disclosed in copending appli-'.

cation Serial No. 312,742, filed January 6, 1940, by F. E. Drummond andW. A. Waldie, blown dehydrated castor oil has been used as a substitutefor the costly drying oils previously used in the preparation of wrinklevarnish base. Castor oil in its native state is a nondrying oil. Itschiei constituent, ricinoleic acid, has only one double bond andtherefore does not have the reactivity necessary to impart drying powerto the oil. It

does contain, however, a hydroxyl group and it has been found possibleto remove the hydroxyl group, together with an adjoining hydrogen, inthe form of water from ricinoleic acid 'or its triglyceride and in sodoing to introduce a second double bond into the molecule. Castor oilcan thus be converted into a drying oil by effecting a substantiallycomplete dehydration by removing one molecule of water from each radicalof ricinoleic acid or a total of three molecules from the tri-glycerideof this acid.

While the dehydration of castor oil resultsin an increase in its dryingcapacity, the dehydrated product does not possess the marked dryingcharacteristics of tung and oiticica oils, nor does it exhibit thedecided wrinkling tendencies of these oils. However, dehydrated castoroil may be converted into a valuable wrinkling oil by blowing.

Other drying and semidrying oils such as linseed, perilla and soya beenhaving double bonds in their structure, or mixtures of such oils, may

be given marked wrinkling tendencies by blowing. It is interesting toconsider the type of reaction which may take place when an oil is blownwith air at elevated temperature and to compare these possible reactionswith those which may occur when an oil is kettled or bodied by theapplication of heat.

When an oil such as linseed oil, for example, is

heated in a kettle, the reactions which take place may be generallyconsidered to be of a polymerization or association type involvingeithei direct chemical union by primary valence forces,

and gradually the oil becomes less and less soluble or dispersible inmineral spirits and other types of oil solvents. a solid gelcharacterized by substantial insolubility in mineral spirits and othertypical oil solvents.

On the other hand, if oxygen (as in the form of air) wereto bereactedwith the linseed oil under the influence of heat, as is the case in theusual blowing operation, it is possible that a peroxide is formed whichlater on may be rearranged to form alpha-hydroxy ketones.

It is considered that when the oil is simply heat bodied or kettled, thereaction which takes place is largely polymerization, but when the oilis subjected to blowing polymerization as well as oxidation may possiblytake place.

When the blowing operation is carried out at temperatures lower thancustomary, it is believed that oxidation preferentially takes place anda finished product is obtained which has distinguishing characteristicsas compared with the same oil when subjected to the ordinary type ofblowing.

Kettling or heat bodying is employed primarily for the purpose ofreducing the time required for cooking a given batch of varnish andthereby increasing the output of the varnish kettle, while blowing isemployed not only to'increase the viscosity of the oil but to change itschemical constitution by the addition of oxygen molecules. However, thetemperature at which blowing is generally carried out results in theabsorption by the oil of large amounts of air which remains chemicallyuncombined and intermolecularly dispersed. This absorbed air, duringstorage of the oil, causes auto-oxidation and a gradual increase in theviscosity of the oil and ultimately leads to partial gelation andprecipitation thereof. It will be understood by those skilled in the artthat when the oil in a coating composition gels and precipitates out,this causes blobs or agglomerates and a lack of uniformity in theconsistenty of the oil. These blobs" serve to plug up the spray head ofspray guns with which it is applied and, consequently, a coatingcomposition exhibiting such an undesirable characteristic is consideredan inferior product.

As has been noted above, dehydrated castor oil when subjected toblowing, as well as natural drying and semidrying oils possessing doublebonds in their structure, may be utilized in wrinkle coatingcompositions if previously subjected to blowing; however, it has beenconsidered impossible hitherto to incorporate more than small amounts ofsubstantially nondrying oils inwrinkle coating compositions because oftheir extreme resistance to oxidation, since rapid surface oxidation isa prerequisite for wrinkle formation.

According to the present invention, it is possible to utilizenonconjugated oils having low oxidation propensity in the production ofwrinkle coatin compositions. The oils which are made available for useaccording to the present invention include oils which are plentifuilyavailable from domestic sources and the quality and price of which arenot subjected to extreme fluctuations. It is thus possible, by thepractice of the present invention, to free the industry from thenecessity of using costly, ununiform, foreign oils, the supply of whichis limited and undependable.

The present invention will be-more clearly understood by reference tothe following description taken in connection with the annexed drawing,in which:

The oil will finally set to i is a jacketed kettle provided with anagitator Ii driven by a motor l2 through a speed reducer 13. The jacketof the kettle I0 is supplied with steam or othe heating medium throughinlet pipe I4 and the condensate is removed through condensate line l5and steam trap I8.

The kettle I0 is provided with a manhole I1 for charging the kettle anda drain l8 provided with a valve IQ for emptying the kettle. The kettleIii is further provided with a distillate outlet line 20 connected witha condenser. 2| through which cooling water, or other fluid,is-circulated through inlet pipe 22 and outlet pipe 23. The condensatefrom the condenser 2! is returned to the kettle through condensate line24, valve 25, gooseneck or liquid seal 26 and line 21. A by-pass 28,provided with a valve 29, connects with condensate line 24 and areservoir or storage tank 30. A pump -3l is connected to the reservoir30 through line 32 and discharges fiuid taken from reservoir 30 throughline 33, valve 34 and line 35, the latter being connected with line 21.

In the practice of my invention an oil having nonconjugated double bondsin its structure is caused to react at elevated temperature with analcoholic solution of an alkali metal hydroxide under reflux and thereaction is continued until a sample withdrawn from the reaction vesselshows the desired-degree of conjugation as determined by any suitablemethod. When this stage of the reaction has been reached the alcohol isremoved by distillation and recovered for re-use by condensation. Thefatty acids are precipitated out by acidifylngthe mixture and washing tore move foreign matter. To the residue there is then added a-suitablequantity of glycerin and the batch heated to bring aboutre-esterification of the fatty acids to a mono-, di-, or tri-glyceride,thus producing a synthetic oil possessing a high proportion ofconjugated double bonds from an oil normally possessing none. Thissynthetic oil may be'used in the manufacture of wrinkle coatingcompositions.

As an alternative procedure, I may react an oil having nonconjugateddouble bonds in its structure with alkali metal alcoholate in alcoholsolution. The reaction is carried out at elevated temperature underreflux for time sufficient to produce the desired degree ofconjugation.The alcohol is then recovered for re-use by condensation and the residuetreated as hereinbefore described to isolate the fatty acids, which arethen re-esterified to produce a synthetic oil usable in wrinkle coatingcompositions.

A further and preferred procedure is to react an oil with alcoholicalkali metal hydroxide at elevated temperature and under reflux for timesufficient to produce thedesired degree of conjugation of the doublebonds in the structure of the oil. When this has been attained, thealcohol is removed by distillation and saved for future use. The fattyacids are isolated as hereinbefore described, a polybasic acid oranhydride and a ,polybasic alcohol added, .and the whole heated coholatein alcohol solution. The reaction is carried out under reflux for timesuflicient to produce the desired degree of conjugation. The alcohol isthen removed by distillation and saved for future use. The fatty acidsare then precipitated and separated out and there is added to them apolycarboxylic acid or anhydride such as malelc acid or phthalic acid ortheir anhydrides and a polyhydric alcohol such as glycerol or glycol andthe whole heated further until a drop deposited on glass shows clear.Thereupon there is added to the batch a quantity of a top drier,together with hydrocarbon diluent in quantity sufilcient. to give asprayable product. The resulting product, when applied on a surface andbaked, will, likewise, give a hard, tough, wrinkled film of uniform andpleasing texture.

Without thereby intending to limit my invention to the specific detailsdisclosed, I shall now describe some typical procedures which may befollowed advantageously in the practice of my invention.

Example I I2 is set in motion to drive the agitator I I through speedreducer l3; and steam is introduced into the jacket of kettle l throughline M for the purpose of heating the contents of the kettle.

As the temperature of the batch increases albeing approximate. Themixture is agitated continuously and preferably in theabsence of anoxidizing atmosphere until the reaction has proceeded to the desiredextent as indicated by the acid number of the product obtained. Whenthis point has been reached the batch is permitted to cool down to a.temperature of approximately 350 F., whereupon there is added to thebatch a quantity of top drier such as cobalt naphthenate, together withhydrocarbon diluent in quantity suficient to reduce the consistency ofthe batch to a sprayable condition at room tem-' perature. The amount oftop drier". necessary will be in the neighborhood of from 0.5 to 3 percent depending on the texture required. The composition resulting from.the above procedure, when applied on a surface and baked, will yield atough, hard, wrinkled surface of uniform and pleasing texture.

It will be understood that a concentrated alcoholic solution ofpotassium hydroxide may be added to the kettle 10 through manhole I1 andthe balance of the alcohol required added by pump 31 through lines 32and 33, valve 34 and lines 35 and 21 (valve being closed) from reservoir30. On the other hand, an alcoholic KOH solution of the desiredconcentration may be placed in the reservoir and introduced into thekettle by pumping.

Example II- together with an excess of sodium ethylate in cohol vaporswill be driven out of the kettle through line 20 and into condenser 2|which is cooled by introducing water through line 22 and discharging itthrough line 23. Condensate will leave the condenser 2| through line 24,and passing through valve 25 (which will be open), gooseneck 26 and line21 will be returned to the kettle 1 I0. This will serve to maintain aconstant or uniform concentration of alcohol in the batch.

It will be understood that valves 29, 34 and 19 remain closed throughoutthis operation.

Samples are withdrawn from the kettle ID from time to time and thedegree of conjugation is determined on them. This may be done, forexample, by determining the iodine number, or the diene value, or thesamples may be spectrographically analyzed. When the required or desireddegree of conjugation has been reached, valve 29 is opened and valve 25is closed, whereby the condensate from condenser 2| will flow throughlines 24 and 28 and valve 29 to reservoir 30, wherein it is stored forfuture use. The contents of the kettle may then be transferred to aseparate vessel for the purpose of separating the treated soap from theresidual saponifying reagent and for the purpose of isolating the fattyacids; however, these operations, if desired, may be carried out in thekettle l0, although this would not be good commercial practice.

The treated soap resulting from the above procedure is, acidified, andthe precipitated fatty acids are separated. These fatty acids aretransferred to a vessel such as jacketed kettle l0 and there subjectedto the action of heat. When the temperature has reached about 400 F.glycerol andv phthalic anhydride are added in quantity sufflcient toproduce a mixture comprising by weight 60 parts of glycerol, 120 partsof phthalic anhydride, and 102 parts of fatty acids, all values alcoholsolution in which the ethylate content is 20 per cent, and the molalproportion of oil to alkali may be of the order of from 1:4 to TF5.

The batch is treated in the same manner as hereinbefore described inExample I.

The treated soap resulting from the treatment of the oil with thealcoholate is acidified to separate the fatty acids. These fatty acidsare treated in the same manner as described in Example I and the productresulting therefrom will be a wrinkle coating composition havingsubstantially the same characteristics as the wrinkle coatingcomposition resulting from the practice of the method described inExample I.

Ewample III A quantity of peanut oil is placed in the kettle,

ing the saponification reaction and to bring about re-esterification ofthe resulting free fatty acids by the glycerin which separated onsaponification of the oil.

The temperature is then reduced to approximately 400 F., whereupon thereis added to the kettle glycerol and phthalic anhydride in quantitysufficient to yield the ratio set forth in Example I. The mixture isagitated continuously and treated further as indicated in Example I.

The resulting composition will yield a tough, hard, wrinkled surface ofuniform texture when applied on a surface and baked.

Example IV A quantity of cottonseed oil is placed in the kettle,together with a quantity of potassium hydroxide dissolved in glycerolsuflicient to yield a molal'proportion of oil to hydroxide of the orderof from 1:4 to 1:5. The amount of glycerol to be used should besuflicient to provide thorough distribution and intermingling of the oiland hydroxide.

The reaction is carried out under reflux at a temperature ofapproximately 400 F. until a sample withdrawn from the batch indicatesthat the desired degree of conjugation of the oil has been obtained. Thesoap resulting from the above operation is acidified to' precipitate thefatty acids which are then further treated at elevated temperature in.the presence of polyhydric alcohol and polybasic acid as set forth inExample I.

It will be understood that in the practice of' my invention 1 mayutilize alkali metal alcoholates of various sorts such as ethylate,methylate, butylate, isoamy'late, etc., and that any of the alcoholsoluble alkali metals may be employed, although I prefer to use sodiumand potassium alcoholates.

It will be also understood that in the practice of my invention I canmake use of other polyhydric alcohols in place of glycerol, as forexample, polyglycerol, the glycols, polyglycols, mannitol, sorbitol,etc.; and that other polycarboxylic acids such as ma1ic,maleic, fumaric,succinic, citric, tartaric, mucic, benzoyl-benzoic, and their anhydridesmay be used in place of the phthalic anhydride employed in the examples.

The selection of thinner is not critical although preference should begiven to those products of high volatility such as toluol, xylol, lightnaphtha, etc., all of which may be used satisfactorily in the practiceof my invention.

Likewise, many different driers may be used so long as they are of thetype possessing the inherent characteristic of bringing about a rapidformation of a 'skin on the exposed surface of the film in order tocause the changes in volume between the surface of the film and theinterior thereof which lead to the production of wrinkled surfaces. atetype of drier, characterized by ready solubility, proves very suitablefor this purpose.

It will be appreciated from what has been The resinate, linoleate, ornaphthenstated hereinb'efore that in the practice of my invention I makeuse of oils, the nature of which in their natural state is such as torender them unsuitable for use in rapid drying coating compositions,andthat according to the method of my invention, I am ablesatisfactorily and economically to convert such oils into synthetic oilsor fatty acids which are eminently well adapted for use in themanufacture of wrinkle coating compositions. Furthermore, it will beappreciated by those skilled in the art that wrinkle compositions suchas produced according to the method of my invention may be produced fromoils plentifully available from domestic sources and the price andquality of which are not subjected to marked fluctuations. In addition,the wrinkle coating compositions produced according to the method of myinvention' yield hard, tough films which are adapted to form a surfaceof uniform wrinkled texture when baked.

It will be understood that the apparatus illustrated in the annexeddrawing is purely illustrative and that I do not limit myself to the useof such an apparatus in the practice of the method of 'my invention. Inaddition, an theories advanced herein are offered simply as explanatorymatter and not as limitations on my invention.

Furthermore, it will be understood that while I have herein set forthcertain specific embodiments of my invention, it is not my intention tohave it limited to or circumscribed by the specific details of procedureand proportions indlcated, since my invention is adapted to be modifiedaccording to individual preference and conditions within'the scope ofthe appended claim.

I claim: l A wrinkle coating composition comprising a resin resultingfrom the reaction at 400 F. of parts of glycerol, parts of phthalicanhydride and 102 parts of fatty acids; from 0.5 to 3 percent of a topdrier; and hydrocarbon diluent; said fatty acids having been produced bythe treatment of an oil selected from the group consisting of cottonseedoil, corn oil, and peanut oil with an alcoholic solution of an alkalimetal hydroxide under reflux to cause rearrangement of the nonconjugateddouble bonds in the acid radicals of the oil to conjugated double bondsand to cause formation of fatty acid soaps, and then isolating the fattyacids.

, E. L. LUAcEs.

